Use of norbornyl oxyacetaldehyde in augmenting or enhancing the aroma of detergents

ABSTRACT

Described is a compound having the structure: ##STR1## a norbornyl oxyacetaldehyde, prepared by oxidizing the norbornyl oxyethanol compound having the structure: ##STR2## using air or oxygen and a silver or copper chromite catalyst; and organoleptic uses of such oxidation product in the field of perfumery, colognes and perfumed articles (e.g. perfumed plastics, solid or liquid anionic, cationic, nonionic or zwitterionic detergents, fabric softener compositions or drier-added fabric softener articles).

This is a divisional of application Ser. No. 303,012, filed Sept. 17,1981, now U.S. Pat. No. 4,354,043.

BACKGROUND OF THE INVENTION

The instant invention relates to the compound which is a norbornyloxyacetaldehyde having the structure: ##STR3##

Inexpensive chemical compounds which can provide intense andlong-lasting woody, lavender-like, rosemary-like, green aroma withrosemary-like, lavandin-like, woody, natural pine oil and freshherbaceous nuances on dry-out are desirable in the art of perfumery.Many of the natural materials which provide such fragrances andcontribute such desired nuances to perfumery compositions are high incost, unobtainable at time, vary in quality from one batch to anotherand/or are generally subject to the usual variations of naturalproducts.

There is, accordingly, a continuing effort to find synthetic materialswhich will provide, enhance or augment the fragrance notes provided bynatural essential oils or compositions thereof. Unfortunately, many ofthe synthetic materials either have the desired nuances only to arelatively small degree, or they contribute undesirable or unwanted odorto the compositions.

Although norbornyl derivatives are known in the art for producing pineyaromas such as, for example, those disclosed in U.S. Pat. No. 4,153,811issued on May 8, 1979, the inexpensive norbornyl oxyacetaldehyde type ofcompound has heretofore been unknown.

Thus U.S. Pat. No. 4,153,811 discloses the use of substituted norbornanederivatives of the genus of compounds having the structure: ##STR4##wherein each of the dashed lines represents a carbon-carbon single bondor a carbon-carbon double bond with the proviso that at least one of thedashed lines is a carbon-carbon single bond; wherein n is 0 or 1 withthe proviso that n is 1 when both dashed lines are carbon-carbon singlebonds and n is 0 when one of the dashed lines is a carbon-carbon doublebond; wherein R₁ and R₂ are each the same or different hydrogen or loweralkyl; wherein Y is: ##STR5## wherein Z is one of the moieties: ##STR6##wherein R₃ and R₄ are each alkyl; wherein R₇, R₈ and R₁₀ are each thesame or different hydrogen or lower alkyl; wherein R₉ and R₉ ' takenseparately are the same or different lower alkyl, or taken together islower alkylene; wherein the dotted line represents a carbon-carbonsingle bond or a carbon-carbon double bond; and wherein each of the wavylines represents, in the alternative, exo or endo isomers.

U.S. Pat. No. 3,852,358 issued on Dec. 3, 1974 discloses a process forproducing 2-acetyl-3,3-dimethyl-5-norbornene in both the exo and endoforms which have uses in perfumery and other fragrance applications.These compounds have the structures: ##STR7## These compounds, producedby reaction of cyclopentadiene with mesityl oxide, are startingmaterials for producing a number of the compounds of our invention.However, the compounds of our invention have unexpected, unobvious andadvantageous properties when compared with the2-acetyl-3,3-dimethyl-5-norbornene of U.S. Pat. No. 3,852,358.

U.S. Pat. No. 3,942,761 discloses the use in perfumery of4-(2'-norbornyl)-2-butanones having the structure: ##STR8## wherein R₁is hydrogen or methyl and R is hydrogen or lower alkyl containing from 1to 8 carbon atoms. Such compounds have structures which are different inkind from the structures of the compounds of our invention. Alsodisclosed as intermediates for producing the foregoing compounds arecompounds having the generic structure: ##STR9## wherein the dotted lineis a carbon-carbon single bond or a carbon-carbon double bond. Inaddition, the following reaction sequence is set forth therein:##STR10##

Arctander, "Perfume and Flavor Chemicals", 1969, Vol. 1, discloses theuse in perfume compositions and in foodstuff flavors of "fenchone","fenchyl alcohol", "camphene carbinol", and "camphene carbinyl acetate",thus:

(i) "1385: FENCHONE laevo-Fenchone (dextro- is known but less common asa fragrance material). 1,3,3-trimethyl-2-norbornanone. 1,3,3-trimethylbicyclo-1,2,2-heptanone-2. ##STR11## Warm-camphoraceous, powerful anddiffusive, basically sweet odor. Warm, somewhat burning and bitter tastewith a medicinal note. This ketone finds some use as a masking odor inindustrial fragrances. It is also used in the reconstruction of fenneloil and a few other essential oils. In spite of its rather unpleasanttaste, it is used in various berry complex flavors, in spice complexesand in certain types of liquor flavoring. The concentration used isabout 0.1 to 5 ppm in the finished product."

(ii) "1387: FENCHYL ALCOHOL 1,3,3-trimethyl-2-norbornanol.1,3,3-trimethyl bicyclo-1,2,2-heptanol-2. 2-fenchanol. Fenchol.##STR12## The racemic alpha-fenchol has a somewhat lower melting point,and the beta-fenchols are all liquid at room temperature. Fenchol madeby reduction of fenchone from cedarleaf oil is usually a mixture ofseveral isomers, including the crystalline alpha-isomers. Thebeta-isomer forms a crystalline hydrate which may be sold at roomtemperature. Almost insoluble in water, soluble in alcohol, misciblewith oils. Powerful and diffusive, camphor-like but sweeter and morecitrus-like almost lime-like color with more or less of an earthy-drycharacter, according to the composition and isomer-ratio. The taste issomewhat bitter-lime-like, camphoraceous and slightly woody-musty. Thisinteresting alcohol (or mixed alcohols) finds use in perfumecompositions ranging from woody or herbaceous to citrus-lime and evencertain floral types. It produces power and "lift" to floral fragrances,and solid background to lime and other citrus bases, having theadvantage over the terpenes in being very stable in soap. Fenchylalcohol is also used in flavor compositions such as strawberry and otherberries, lime and spice, etc. The concentration is normally low, e.g.0.2 up to 5 ppm in the finished product."

(iii) "1028: 3,3-DIMETHYL-Δ², beta-NORBORNANE-2-ETHANOL. "Camphenecarbinol". ##STR13## Sweet, camphoraceous, warm and soft odor with awoody undertone. Upon standing it may develop an odor resembling that ofcelluloid.

Although rarely offered commercially, this chemical could find some usein perfume compositions of the woody, oriental and orissy type, in newvariations of pine fragrances, and in various soap and detergentperfumes".

(iv) "1029: 3,3-DIMETHYL-Δ² -beta-NORBORNANE-2-ETHYLACETATE "Camphenecarbinyl acetate". ##STR14## Mild and sweet-woody odor with afloral-piney undertone. The commercial products are probably notwell-defined single chemicals, and great variations in odor have beenobserved.

This ester has been developed in line with the research on sandalwoodtype odors. The parent alcohol "camphene carbinol" was once considereduseful as a sandalwood type material, but it has found more use as asweetening and enriching ingredient in sophisticated pine fragrances.The title ester finds limited use in perfume compositions of woodycharacter, fougeres, pine fragrances, etc. and it blends very well withthe cyclohexanol derivatives, ionones, isobornylacetate, nitromusks,etc.".

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile of the reaction product of Example I prior todistillation (conditions: 10'×1/4" SE-30 column programmed at 160° C.isothermal).

FIG. 2 is the GLC profile of the distillation product of the reactionproduct of Example I containing the compound having the structure:##STR15##

FIG. 3 is the NMR spectrum for the distillation product of Example Icontaining the compound having the structure: ##STR16##

FIG. 4 is the infra-red spectrum for the distillation product of thereaction product of Example I containing the compound having thestructure: ##STR17##

FIG. 5 is a schematic diagram of the apparatus used in order to carryout the oxidation reaction of Example I in order to effect the chemicalreaction: ##STR18## showing the production of the norbornyloxyacetaldehyde of our invention.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example I, thereaction carried out in the apparatus, the diagram for which is in FIG.5. Peak 201 of the GLC profile contains the compound having thestructure: ##STR19##

FIG. 2 is the GLC profile for the distillation product of the reactionproduct of Example I (conditions: 10'×1/4" SE-30 column programmed at160° C. isothermal). Peak 301 represents the compound having thestructure: ##STR20## Peak 302 represents the alcohol reactant having thestructure: ##STR21##

FIG. 5 represents a schematic diagram of the process equipment forcarrying out the process of Example I for effecting the reaction:##STR22## wherein the alcohol having the structure: ##STR23## isoxidized over a silver catalyst to form the aldehyde having thestructure: ##STR24##

Organic reactant feed 100 which is the alcohol having the structure:##STR25## held in holding tank 101 calibrated according to calibrationapparatus 107 using pump 104 is fed through tube 109 simultaneously withwater feed 103 held in holding tank 102 calibrated by calibrationapparatus 106 (using pump 105 and tube 108 for the water feed) throughvaporizers 110 (for the alcohol feed) and 111 (for the water feed)(wherein the mixture is heated) and then through heated tube 112equipped with pressure gauge 113 and release value 114 into reactiontube 17 containing catalyst 18 (the reaction tube being heated using acylindrical furnace 16 at 115). The catalyst bed 18 is rotated as aresult of the rotation of rotatable rod 19. simultaneously air held inpressurized cylinder 120 under pressure and nitrogen held in pressurizedcylinder 121 uppumped through regulator 119 (for the air) and regulator122 (for the nitrogen) and filter 118 (for the air) and filter 123 (forthe nitrogen) using mass flow controller 117 (for the air) and mass flowcontroller 116 (for the nitrogen) into heated tube 112 thereby creatinga mixture at 112 of air, nitrogen, alcohol having the structure:##STR26## and water vapor. The reaction mixture passes through catalystbed 18 through condensation coil 6 which is cooled using cooling waterentering the heat exchange 5 at location 4 and exiting at location 7.The condensed reaction product consisting essentially of the compoundhaving the structure: ##STR27## is retained in flask 2 at location 1,flask 2 being cooled using ice bath 3. Vacuum source 14 is used toassist the flow of the organic feed, the water feed, the nitrogen andthe air or oxygen through reactor 17 into flask 2. Volatiles arecondensed in flask 12 cooled by dry ice bath 13 and in the Dewar dry icebath 15. Assisting in the cooling of the volatiles not retained in flask2 is heat exchanger 9 wherein water is used as a coolant entering theheat exchanger at location 10 and existing from the heat exchanger atlocation 11.

THE INVENTION

The present invention provides the compound having the structure:##STR28## The compound of our invention produced according to theprocess of our invention is capable of augmenting, enhancing orproviding woody, lavender-like, rosemary-like, green aroma withrosemary-like, lavandin-like, woody, natural pine oil and freshherbaceous nuances on dry-out in perfume compositions, colognes andperfumed articles (e.g. perfume polymers, solid or liquid anionic,cationic, nonionic or zwitterionic detergents, fabric softener articles,drier-added fabric softener articles, fabric softener compositions,cosmetic powders, hair preparations, shampoos and the like).

The compound having the structure: ##STR29## may be in either exo orendo form, that is, having the structures: ##STR30## or this compoundhaving the structure: ##STR31## can represent mixtures of both compoundshaving the structures: ##STR32##

The compound of our invention is produced by first reacting the compoundhaving the structure: ##STR33## with oxygen or air according to theoxidation reaction: ##STR34## which is preferably carried out inapparatus described in the "Detailed Description of the Drawings"section of the instant specification, supra, and schematically shown inFIG. 5. The oxidation may use either air or oxygen. The oxidationcatalyst may either be silver or copper chromite (CuCro₃).

The reaction temperature may vary from 200° C. up to 500° C. but thetemperature is dependent upon the desired yield and required residencetime of the reactant compound having the structure: ##STR35## in contactwith the solid catalyst. Necessarily, the reaction is vapor phase andthe surface area of catalyst and flow rate of reactant as well asresidence time and reaction temperature and pressure are all importantvariables which must be optimized in relation to one another if yieldand conversion of product are to be optimized. It is preferred that thereaction be carried out in the presence of water vapor and it is alsopreferred that the water flow rate and flow rate of alcohol reactant beapproximately equal. The gas flow rates may vary between 50 and 400 mlper minute with a preferred oxygen flow rate of 285 ml per minute at atemperature of reaction of 450° C.; a liquid alcohol flow rate of 2 mlper minute and water flow rate of 2 ml per minute. As will be seen froman examination of FIG. 1 (the GLC profile of the reaction product ofExample I) the yield using the foregoing conditions is approximately50%. Separation of the aldehyde reaction product from the alcoholreactant and recycling of the alcohol reactant will, of course, raisethe yield. A higher temperature of reaction, e.g. 500° C. and longerresidence time (e.g. greater distance of travel of reactant throughcatalyst and/or area of contact with catalyst) will raise the yield atapproximately 80%, the higher residence time being approximately 20%greater than what is used in Example I.

The aldehyde compound having the structure: ##STR36## (hereinafterreferred to as the norbornyl oxyacetaldehyde) prepared in accordancewith the process of our invention and one or more auxiliary perfumeingredients including, for example, alcohols, aldehydes other than thenorbornyl oxyacetaldehyde of our invention, ketones, terpenichydrocarbons, nitriles, esters, lactones, natural essential oils andsynthetic essential oils, may be admixed so that the combined odors ofthe individual components produce a pleasant and desired fragranceparticularly and preferably in the pine and lavender fragrances. Suchperfume compositions usually contain (a) the main note or the "bouquet"or foundation stone of the composition; (b) modifiers which round offand accompany the main note; (c) fixatives which include odoroussubstances which lend a particular note to the perfume throughout allstates of evaporation and substances which retard evaporation; and (d)top notes which are usually low-boiling, fresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute their particular olfactory characteristics, however, theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, the norbornyloxyacetaldehyde composition of matter prepared in accordance with theprocess of our invention can be used to alter, modify or enhance thearoma characteristics of a perfume composition, for example, byutilizing or moderating the olfactory reaction contributed by anotheringredient or other ingredients in the composition.

The amount of norbornyl oxyacetaldehyde prepared in accordance with theprocess of our invention which will be effective in perfume compositionsas well as in perfumed articles (e.g. perfumed polymers, anionic,nonionic, cationic or zwitterionic detergents, soaps, fabric softenercompositions, fabric softener articles and hair preparations) andcolognes depends upon many factors including the other ingredients,their amounts of the effects which are desired. It has been found thatperfume compositions containing as little as 0.01% of the norbornyloxyacetaldehyde composition prepared in accordance with the process ofour invention or even less (e.g. 0.005%) can be used to impart alavender, woody and piney aroma with a fresh herbaceous background tosoaps, cosmetics, anionic, cationic, nonionic or zwitterionicdetergents, perfumed polymers, fabric softener compositions, fabricsoftener articles or other products. The amount employed can range up to70% of the fragrance components and will depend on considerations ofcost, nature of the end product, the effect desired on the finishedproduct and the particular fragrance sought.

The norbornyl oxyacetaldehyde composition prepared in accordance withthe process of our invention is useful (taken alone or taken togetherwith other ingredients in perfume compositions) as an olfactorycomponent in detergents and soaps, space odorants and deodorants,perfumes, colognes, toilet water, bath preparations such as creams,deodorants, hand lotions and sun screens; powders such as talcs, dustingpowders, face powders, microporous "perfumed" slow release polymers,(e.g. polyurethane microporous polymers) and the like. When used as anolfactory component in perfumed articles, as little as 0.05% of thenorbornyl oxyacetaldehyde prepared in accordance with the process of ourinvention will suffice to impart a woody, lavender, piney aroma withherbaceous nuances to pine or lavender formulations. Generally no morethan 6% of the norbornyl oxyacetaldehyde composition of our inventionbased on the ultimate end product is required in the perfumed article.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle or carrier for the norbornyloxyacetaldehyde composition prepared in accordance with the process ofour invention. The vehicle can be a liquid, such as a non-toxic alcohol(e.g. ethyl alcohol), a non-toxic glycol (e.g. 1,2-propylene glycol) orthe like. The carrier can also be an absorbent solid such as a gum (e.g.gum arabic or xanthan gum) or components for encapsulating thecomposition (such as gelatin) as by coacervation or polymers such asurea formaldehyde polymers.

It will thus be apparent that the norbornyl oxyacetaldehyde prepared inaccordance with the process of our invention can be utilized to alter,modify or enhance sensory properties, particularly organolepticproperties such as fragrances of a wide variety of consumable materials.

The following Example I sets forth a means for synthesizing thenorbornyl oxyacetaldehyde of our invention. The following Examples IIand following serve to illustrate the organoleptic utilities of thenorbornyl oxyacetaldehyde of our invention.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF NORBORNYL OXYACETALDEHYDE Reaction ##STR37##

Using the apparatus of FIG. 5, a catalytic oxidation of the alcoholhaving the structure: ##STR38## is carried out. Maintaining the silvercatalyst and reaction tube at a temperature of 450° C. (using furnace 16and silver catalyst 18 on shaft 19 in reactor 17) oxygen held in vessel120 is permitted to flow at a flow rate of 230 ml per minute throughregulator 119, filter 118 and mass flow controller 117 through heater112 while at the same time nitrogen at the flow rate of 100 ml perminute is permitted to flow through regulator 122, filter 123 and massflow controller 116 whereupon the nitrogen flow joins the oxygen flowand the combined gasses are fed through heater 112 into reactor 17.Simultaneously, the alcohol having the structure: ##STR39## held inholding tank 101 is pumped through pump 104 into vaporizer 110 throughheating tube 112 along with the oxygen and nitrogen. Simultaneously,water 103 in holding tank 102 is pumped through pump 105 through tube108 into vaporizer 111 and finally through heated tube 112 along withthe oxygen, nitrogen and the alcohol reactant having the structure:##STR40## and finally into the reactor 17 through the silver catalyst 18at 450° C. The flow rate of the alcohol having the structure: ##STR41##is 2 ml per minute (liquid). The liquid flow rate of the water is also 2ml per minute.

The reaction product having the structure: ##STR42## is condensed inheat exchanger 5 at 6 and is collected at location 1 in flask 2 which iscooled by ice bath 3. Volatiles are collected in flask 12 and cooled bydry ice bath 13. A vacuum 14 is applied wherein the final volatiles arenot permitted to escape but are collected at 15.

The detailed description of FIG. 5 is set forth in the DetailedDescription of the Drawings for FIG. 5.

FIG. 1 is the GLC profile for the reaction product prior todistillation. Peak 201 is the peak for the compound having thestructure: ##STR43## (conditions: 10'×1/4" SE-30 column programmed at160° C. isothermal).

FIG. 2 is the GLC profile for the distillation product, bulked fractions5-10 of the distillation product of the reaction product above. Thedistillation is carried out on a 12" stone packed column yielding thefollowing fractions:

    ______________________________________                                                Vapor   Liquid                Weight of                               Fraction                                                                              Temp.   Temp.   Pressure                                                                              Reflux                                                                              Fraction                                Number  (°C.)                                                                          (°C.)                                                                          mm/Hg.  Ratio (grams)                                 ______________________________________                                        1       24/40   24/85   1.2/1.2 9:1   18.3                                    2       60      113     1.2     9:1   2.0                                     3       67      114     1.2     9:1   6.5                                     4       80      114     1.2     9:1   5.1                                     5       80      114     1.2     9:1   6.4                                     6       80      114     1.2     9:1   11.9                                    7       80      114     1.2     2:1   6.6                                     8       82      115     1.2     2:1   9.2                                     9       82      115     1.0     2:1   6.8                                     10      82      115     1.0     2:1   10.2                                    11      81      115     1.0     2:1   11.3                                    12      81      135     1.0     2:1   6.3                                     13      72      182     1.1     2:1   1.4                                     ______________________________________                                    

FIG. 3 is the NMR spectrum for bulked fractions 5-10 of the foregoingdistillation.

FIG. 4 is the infra-red spectrum for bulked fractions 5-10 of theforegoing distillation.

EXAMPLE II PINE FRAGRANCE

The following pine fragrance formulation is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Isobornyl acetate      100                                                    Camphor                10                                                     Terpineol              25                                                     Fir balsam absolute                                                           (50% in diethyl phthalate)                                                                           20                                                     Coumarin               4                                                      Linalool               30                                                     Fenchyl alcohol        10                                                     Anethol                12                                                     Lemon terpenes washed  50                                                     Borneol                5                                                      Galbanum oil           5                                                      Turpentine Russian     150                                                    Eucalyptol             50                                                     2,2,6-trimethyl-1-cyclohexane-1-                                              carboxaldehyde         12                                                     Maltol (1% in diethyl phthalate                                                                      5                                                      Bulked fractions 5-10 of the                                                  distillation product of Example I                                             consisting of the compound having the                                         structure:             28                                                      ##STR44##                                                                    ______________________________________                                    

The norbornyl oxyacetaldehyde prepared according to Example I imparts tothe pine formulation an intense lavender, woody, fresh herbaceous aromaprofile. The pine formulation with the additional intense nuances causedby the use of the product of Example I, has advantageous and unexpectedproperties in the perfume industry.

EXAMPLE III PREPARATION OF COSMETIC POWDER COMPOSITIONS

Cosmetic powder compositions are prepared by mixing in a ball mill 100grams of talcum powder with 0.25 grams of each of the substances setforth in Table I below. Each of the cosmetic powder compositions has anexcellent aroma as described in Table I below:

                  TABLE I                                                         ______________________________________                                        Substance          Aroma Description                                          ______________________________________                                         ##STR45##         A woody, lavender-like, rosemary-like, green aroma                            with rosemary-like, lavandin-like, woody, natural pine                        oil and fresh herbaceous nuances on dry-out.               (bulked fractions 5-10 of the                                                 distillation product of the                                                   reaction product of Example I).                                               Perfume composition produced                                                                     A piney, lavender, woody                                   according to Example II                                                                          and herbaceous aroma.                                      ______________________________________                                    

EXAMPLE IV PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818, issuedon Apr. 6, 1976 incorporated by reference herein) with aroma nuances asset forth in Table I of Example III, are prepared containing 0.10%,0.15%, 0.20%, 0.25%, 0.30% and 0.35% of the substance set forth in TableI of Example III. They are prepared by adding and homogeneously mixingthe appropriate quantity of substance set forth in Table I of ExampleIII in the liquid detergent. The detergents all possess excellent aromasas set forth in Table I of Example III, the intensity increasing withgreater concentrations of substance as set forth in Table I of ExampleIII.

EXAMPLE V PREPARATION OF COLOGNES AND HANDKERCHIEF PERFUMES

Compositions as set forth in Table I of Example III are incorporatedinto colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%and 5.0% in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions;and into handkerchief perfumes at concentrations of 15%, 20%, 25% and30% (in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions).Distinctive and definitive fragrances as set forth in Table I of ExampleIII are imparted to the colognes and to the handkerchief perfumes at alllevels indicated.

EXAMPLE VI PREPARATION OF SOAP COMPOSITIONS

One hundred grams of soap chips (per sample) (IVORY®, produced by theProcter & Gamble Company of Cincinnati, Ohio), are each mixed with onegram samples of substances as set forth in Table I of Example III untilhomogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 8 atmospheres pressure at 180°C. for a period of three hours and the resulting liquids are placed intosoap molds. The resulting soap cakes, on cooling, manifest aromas as setforth in Table I of Example III.

EXAMPLE VII PREPARATION OF SOLID DETERGENT COMPOSITIONS

Detergents are prepared using the following ingredients according toExample I of Canadian Pat. No. 1,007,948 (incorporated herein byreference):

    ______________________________________                                        Ingredient          Percent by Weight                                         ______________________________________                                        Neodol® 45-11 (a C.sub.14 -C.sub.15                                       alcohol ethoxylated with                                                      11 moles of ethylene oxide)                                                                       12                                                        Sodium carbonate    55                                                        Sodium citrate      20                                                        Sodium sulfate, water brighteners                                                                 q.s.                                                      ______________________________________                                    

The detergent is a phosphate-free detergent. Samples of 100 grams eachof this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams ofeach of the substances as set forth in Table I of Example III. Each ofthe detergent samples has an excellent aroma as indicated in Table I ofExample III.

EXAMPLE VIII

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the disclosure of which is incorporated herein by reference),nonwoven cloth substrates useful as drier-added fabric softeningarticles of manufacture are prepared wherein the substrate, thesubstrate coating, the outer coating and the perfuming material are asfollows:

1. A water "dissolvable" paper ("Dissolvo Paper")

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. An outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the substances as set forth in Table I of Example III.

Fabric softening compositions prepared according to Example I at column15 of U.S. Pat. No. 3,632,396 having aroma characteristics as set forthin Table I of Example III, supra, consist of a substrate coating havinga weight of about 3 grams per 100 square inches of substrate; a firstcoating located directly on the substrate coating consisting of about1.85 grams per 100 square inches of substrate; and an outer coatingcoated on the first coating consisting of about 1.4 grams per 100 squareinches of substrate. One of the substances of Table I of Example III isadmixed in each case with the outer coating mixture, thereby providing atotal aromatized outer coating weight ratio to substrate of about 0.5:1by weight of the substrate. The aroma characteristics are imparted in apleasant manner to the head space in a dryer on operation thereof ineach case using said dryer-added fabric softener non-woven fabrics andthese aroma characteristics are described in Table I of Example III,supra.

EXAMPLE IX HAIR SPRAY FORMULATIONS

The following hair spray formulation is prepared by first dissolvingPVP/VA E-735 copolymer manufactured by the GAF Corporation of 140 West51st Street, New York, N.Y., in 91.62 grams of 95% food grade ethanol.8.0 grams of the polymer is dissolved in the alcohol. The followingingredients are added to the PVP/VA alcoholic solution:

    ______________________________________                                             Dioctyl sebacate          0.05 weight percent                                 Benzyl alcohol            0.10 weight percent                                 Dow Corning 473 fluid                                                         (prepared by the Dow Corning                                                                            0.10 weight percent                                 Corporation)                                                                  Tween 20 surfactant                                                           (prepared by ICI America  0.03 weight percent                                 Corporation)                                                                  One of the perfumery sub-                                                     stances as set forth in                                                       Table I of Example III, supra                                                                           0.10 weight percent                            ______________________________________                                    

The perfuming substances as set forth in Table I of Example III addaroma characteristics as set forth in Table I of Example III which arerather intense and aesthetically pleasing to the users of the soft-feel,good-hold pump hair sprays.

EXAMPLE X CONDITIONING SHAMPOOS

Monamid CMA (prepared by the Mona Industries Company) (3.0 weightpercent) is melted with 2.0 weight percent coconut fatty acid (preparedby Procter & Gamble Company of Cincinnati, Ohio); 1.0 weight percentethylene glycol distearate (prepared by the Armak Corporation) andtriethanolamine (a product of Union Carbide Corporation) (1.4 weightpercent). The resulting melt is admixed with Stepanol WAT produced bythe Stepan Chemical Company (35.0 weight percent). The resulting mixtureis heated at 60° C. and mixed until a clear solution is obtained (at 60°C.). This material is "COMPOSITION A".

Gafquat® 755 N polymer (manufactured by GAF Corporation of 140 West 51stStreet, New York, N.Y.) (5.0 weight percent) is admixed with 0.1 weightpercent sodium sulfite and 1.4 weight percent polyethylene glycol 6000distearate produced by Armak Corporation. This material is "COMPOSITIONB".

The resulting COMPOSITION A & COMPOSITION B are then mixed in a 50:50 wtratio of A:B and cooled to 45° C. and 0.3 wt percent of perfumingsubstance as set forth in Table I of Example III is added to themixture. The resulting mixture is cooled to 40° C. and blending iscarried out for an additional one hour in each case. At the end of thisblending period, the resulting material has a pleasant fragrance asindicated in Table I of Example III.

PATENTS INCORPORATED HEREIN BY REFERENCE

The following patents referred to supra are hereby incorporated hereinby reference:

U.S. Pat. No. 3,632,396

U.S. Pat. No. 3,948,818

Canadian Pat. No. 1,007,948

What is claimed is:
 1. A process for augmenting or enhancing the aromaof a perfumed article which is a solid or liquid anionic, cationic,nonionic or zwitterionic detergent comprising the step of adding to asolid or liquid anionic, cationic, nonionic or zwitterionic detergentbase an aroma augmenting or enhancing quantity of the norbornyloxyacetaldehyde having the structure: ##STR46##